Process for the production of



United States Patent RROCESS FOR THE PRODUCTION OF Z-HY- DROXY-4 METHYL (HYDROXYBENZO)- QUINOLINE SULPHONIC ACIDS Rudolf Diirig, Basel, Switzerland, assignor to J. R. Ge'igy A.-G.,.Basel, Switzerland, a Swiss firm N0 Drawing. Application August 22, 1955, Serial No. 529,889

Claims priority, application Switzerland September 2, 1954 oline sulphonic acids. These compounds correspond to, the general formula:

n( OBS) It is already known that 2-hydroxy-4-methyl quinolines can be produced from acetoacetyl' derivatives of simple aromatic amines by treatment with dehydrating closing agents. Thus, for example, L. Knorr (B; .1 7, 3543 (1884); see Conrad and Li-rnpach, B. 21', 532- (11888) has produced the HCCtOflCfitYlrZ-IlfiflhtllYl-flfl'lidfi from 2-aminonaphthalene. by means of acetoacetic acid ethyl esterzand. has converted it by treatment with concentrated hydrochloric acid at the boil: into 2-hydroxy-4-methyl-5tfibenzoquinol-ine.

The adaption of the reaction to the aminonaphthole. sulphonic acids which are importantas azo: coupling components has not been known up to now, as. it appeared doubtful whether the coupling, point would be retained under the energetic conditions of the ring, closing condensing reaction.

It has now been found that acetioacetyl, derivatives of aminonaphthole sulphonic acids havingafree o-position to the acetoacetylated amino group can also be subjected to the Knorr reaction and that in; spite of the energetic conditions of the ring closing reaction the derivatives of such aminonaphthole sulphonic acids. which: couple with aromatic diazonium compounds to form azo dyestuffs, can be converted intohydroxy' quinoline sulphonic acids in which the coupling; points are retained. In this manner therefore, valuable couplingcomponentsfor the: production of monoand poly-azo dyestuffs for the dyeing of cotton are obtained in a sample way.

These compounds are produced according to the present invention by treating acetoacetyl compounds of aminonaphthole sulphonic acids having a neighbouring position to the amino group free, withdehydrating, ring closing agents such as, for example, concentrated phosphoric acid, concentrated hydrochloric acid and in particular, concentrated sulphuric acid. Generally, the ring is closed even at room temperature but the most favourable reaction temperatures lie between 40 and 60. In certain cases it is of advantage to add aluminium chloride 2,763,656 Patented Sept. 18, 1956 to the condensing agents named or to perform the reaction in an aluminium chloride-sodium chloride melt.

The hydroxybenzoqui-noline sulphonic acids are obtained in very good to satisfactory yields.

The acetoacetylaminonaphthole' sulphonic acids used as starting products according to the present invention are obtained by the usual .known methods. They can be produced, for example, by condensing aminonaphthole sulphonic acids with diketenes, but also acetoacetic acid ethyl esters canbe usedinsteadof diketenes.

The following aminonaphthole sulphonic acids can be used for example; 2-amino-5-naphthole-7-sulphonic acid, 2-amino-8-napht-hole-6-sulphonic acid or 2-amino-6- naphthole-S-sulphonic acid, from the acetoacetyl derivatives of. which 2-hydroxy-4-methyl-5.6-(hydroxybenzo)- quinoline sulphonic acids are obtained after ring closure.

If however, substitution products of l-aminonaphthalene are. used, e. g. 1-amino-5-naphthole-7-sulphonic acid, 1ramino-8-naphthole-6-sulphonic acid, l-amino-8-naphthole-3.-6-disulphonic acid or 1-amino-3-naphthole-4.6- disulphonic acid, then 2-hydroxy-4-methyl-7.8-(hydroxyben-z oyquinoline sulphonic acids are obtained; as end products.

The followingexamples illustrate the invention without limiting it. in any way. Wherenot otherwise stated, parts are given as parts by weight and the temperatures are in degrees Centigrade. The relationship of parts by weight to parts by volume is as that of kilogrammes to litres.

Example I SlOgH HOP 32.3. parts of 2-acetoacetylamino-5-naphthole7-sulphonic' acid are dissolved in ZOO parts of 98% sulphuric acid at room temperature whereupon the 2-hydroxy-4- methyl-5.6-(3-hydroxybenzo)-quinoline-5'-sulphonic acid whichforms: while splitting; oil water and ring closure begins to precipitate. The whole is stirred for 12 hours at30" until no more starting product can be traced, then poured into ice water and the reaction product is separated by filtration from the sulphuric acid mother lye. In order to separate the quinoline derivative from slight amounts of Z-amino-S-naphthole-7-sulphonic acid which form during the reaction of the splitting off of the acetoacetyl group, the filter cake is dissolved in 1000 parts of water at 80 and the amount of sodium carbonate necessary to form the odium salt, whereupon, after the addition of parts of sodium chloride, on cooling the product precipitates in, the form of fine yellow needles and can be isolated by filtration.

The sodium salt of 2-hydroXy-4-methyl-5.6-(3-hydroxy-benzo)-quinoline-5-sulphonic. acid obtained in a good yield in this manner is, after drying, a yellow powder which as a solid body and in soda alkaline solution has a strong yellow fluorescence in ultra-violet light. This is in contrast to 2'-amino-5 naphthole-7 sulphonic acid which-1 has abluefluorescence and to 2-acetoacetylamino- 5-naphthole:-7-sulphonic acid which does not fluoresce.

If? in this. example the sulphuric acid is replaced by the same amounts of phosphoric acid 84% or hydrochloric acid. 30%. and the reaction temperature is raised to 40 and otherwise the same procedure is followed, then satis factory yields of the quinoline derivative are also obtained.

In addition, the reaction can also be performed at 150 in an aluminium chloride/ sodium chloride melt, in which case the quinoline derivative is isolated in a manner similar to that described above.

Example 2 Hols OH \CH /COH N 32.2 parts of 2-acetoacetyl-8-naphthole-6-sulphonic acid are dissolved in 200 parts of 98% sulphuric acid at room temperature and the solution is gradually warmed to 50. It is stirred for 20 hours at this temperature until no more starting product can be traced and then poured into 200 parts of ice and water. The reaction product which precipitates is filtered oil and the residue is re-dissolved as described in Example 1 to remove the slight amounts of Z-amino-S-naphthole-6-sulphonic acid. In this way a good yield of the sodium salt of 2-hydroxy-4-methyl-56- good yield of the sodium salt of 2-hydroXy-4-methyl-7.8-

(6'hydroxybe-nzo)-quinoline 4 sulphonic acid is obtained. It crystallises into almost colourless needles and as a solid body and in soda alkaline solution it fluoresces yellow in ultra-violet light.

If, instead of sulphuric acid, an aluminium triethylamine melt is used as ring closing medium and the reaction is performed at 80, then the quinoline derivative is also obtained.

2-hydroxy-4-methyl-7.8-(3-hydroxybenzo) quinolinc- 6' or -5-sulphonic acid or 2-hydroxy-4-methyl-7.8-(3- 'hydroXybenzo)-quinoline 6.5 disulphonic acid are obtained under the same conditions from l-acetoacetylamino-8-naphthole-5- or -6-sulphonic acid or from 1- acetoacetylamino-8-naphthole-4.6-disulphonic acid respectively. The yields are satisfactory. These compounds I also have a yellow fluorescence when exposed to ultra- (6'-hydroxybenzo)-quinoline-4-sulphonic acid is obtained Which crystallises out in the form of fine yellow needles. As a solid body and in soda alkaline solution it fluoresces yellow under the ultra-violet lamp.

' If in this example the sulphuric acid is replaced by the same amounts of phosphoric acid 84% or hydrochloric 0 acid 30% and otherwise the same procedure is followed,

then satisfactory yields of the quinoline derivative are also obtained.

Example 3 Example 4 C-OH HO 32.3 parts of 1-acetoacetylamino-S-naphthole-7-sulphonic acid are dissolved in 200 parts of 98% sulphuric violet rays.

What I claim is:

l. A process for the preparation of a 2-hydroxy-4- methyl-(hydroxybenzo)-quinoline sulphonic acid which comprises treating an acetoacetylaminonaphthole sulphonic acid having a free o-position to the acetoacetylated amino group and containing at most 2 5031-1 groups, with an agent which splits off water and closes the ring.

2. A process for the preparation of a 2-hydroxy-4- methyl-(hydroxybenzo) -quinoline sulphonic acid which comprises treating an acetoacetylaminonaphthole sulphonic acid of the formula:

with an agent which splits off water and closes the ring.

3. The process of claim 1 wherein the agent which splits off water and closes the ring is a strong mineral acid.

. 4. A process for the preparation of a 2-hydroxy-4- methyl-(hydroxybenzo)-quinoline sulphonic acid which comprises treating 2-acetoacetylamino-5-naphthole-7-sulphonic acid with sulphuric acid.

5. A process for the preparation of a 2-hydroXy-4- methyl-(hydroxybenzo)-quinoline sulphonic acid which comprises treating 2-acetoacetyl-8-naphthole-6-sulphonic acid with sulphuric acid.

' 6. A process for the preparation of a 2-hydroXy-4- H methyl-(hydroxybenzo)-quino1ine sulphonic acid which comprises treating Z-acetoacetylamino-6-naphthole-8-sulacid at room temperature, the whole is slowly warmed to 50 and stirred for 12 hours at this temperature. The acetoacetyl compound is completely reacted at the end of this time and the reaction product is isolated and phonic acid with sulphuric acid.

' 7. A process for the preparation of a 2-hydroxy-4- methyl-(hydroxybenzo)-quinoline sulphonic acid which comprises treating l-acetoacetylarnino-5-naphthole-7-sulphonic acid with sulphuric acid.

8. A process for the preparation of a 2-hydroxy-4- methyl-(hydroxybenzo)-quinoline sulphonic acid which comprises treating 1-acetoacetylamino-8-naphthole-5-sulphonic acid with sulphuric acid.

9. A quinoline compound having a formula of the group of formulae consisting of .(nols) on oorr N.

and

m re) wherein n is one of the integers 1 and 2.

10. 2 hydroxy 4 methyl 5.6 (3 hydroxybenzo)- quinoline-5-su1phonic acid.

11. 2 hydroxy 4 methyl 5.6 (6' hydroxybenzoy 5 quino1ine-4'-sulphonic acid.

12. 2 hydroxy 4 methyl 5.6 (4' hydroxybenzo)- quinoline-6-sulphonic acid.

13. 2 hydroxy 4 methyl 7.8 (6' hydroxybenzo)- quino1ine-4-sulphonic acid. 10 14. 2 hydroxy 4 methyl 7.8 (3' hydroxybenzo)- quinoline-6'-sulphonic acid.

No references cited. 

9. A QUINOLINE COMPOUND HAVING A FORMULA OF THE GROUP OF FORMULAE CONSISTING OF: 